Phosphorus-Modified FCC Catalysts

ABSTRACT

Described are fluid catalytic cracking (FCC) compositions, methods of manufacture and use. FCC catalyst compositions comprise catalytic microspheres containing a zeolite, a non-zeolitic component, and a rare earth component. The microspheres are modified with phosphorus. The FCC catalyst composition can be used to crack hydrocarbon feeds, particularly resid feeds containing high V and Ni, resulting in lower hydrogen and coke yields.

TECHNICAL FIELD

The present invention relates to a fluid catalytic cracking catalyst andto a hydrocarbon catalytic cracking process using the catalyst. Moreparticularly, the invention relates to a phosphorus-containing catalystfor processing metal contaminated resid feeds.

BACKGROUND

Catalytic cracking is a petroleum refining process that is appliedcommercially on a very large scale. Catalytic cracking, and particularlyfluid catalytic cracking (FCC), is routinely used to convert heavyhydrocarbon feedstocks to lighter products, such as gasoline anddistillate range fractions. In FCC processes, a hydrocarbon feedstock isinjected into the riser section of a FCC unit, where the feedstock iscracked into lighter, more valuable products upon contacting hotcatalyst circulated to the riser-reactor from a catalyst regenerator.

It has been recognized that for a fluid catalytic cracking catalyst tobe commercially successful, it must have commercially acceptableactivity, selectivity, and stability characteristics. It must besufficiently active to give economically attractive yields, have goodselectivity towards producing products that are desired and notproducing products that are undesired, and it must be sufficientlyhydrothermally stable and attrition resistant to have a commerciallyuseful life.

Excessive coke and hydrogen are undesirable in commercial catalyticcracking processes. Even small increases in the yields of these productsrelative to the yield of gasoline can cause significant practicalproblems. For example, increases in the amount of coke produced cancause undesirable increases in the heat that is generated by burning offthe coke during the highly exothermic regeneration of the catalyst.Conversely, insufficient coke production can also distort the heatbalance of the cracking process. In addition, in commercial refineries,expensive compressors are used to handle high volume gases, such ashydrogen. Increases in the volume of hydrogen produced, therefore, canadd substantially to the capital expense of the refinery.

Improvements in cracking activity and gasoline selectivity of crackingcatalysts do not necessarily go hand in hand. Thus, a cracking catalystcan have outstandingly high cracking activity, but if the activityresults in a high level of conversion to coke and/or gas at the expenseof gasoline the catalyst will have limited utility. Catalytic crackingin current FCC catalyst is attributable to both the zeolite andnon-zeolite (e.g. matrix) components. Zeolite cracking tends to begasoline selective, while matrix cracking tends to be less gasolineselective.

In recent years, the oil refining industry has shifted to processing alarger quantity of residual (resid) and resid-containing feeds due tochanges in the price structure and availability of crude oil. Manyrefiners have been processing at least a portion of residual oil intheir units and several now run a full residual oil cracking program.Processing resid feeds can drastically alter yields of valuable productsin a negative direction relative to a light feed. Aside from operationaloptimizations, the catalyst has a large impact on product distribution.Several factors are important to resid catalyst design. It is highlyfavorable if the catalyst can minimize coke and hydrogen formation,maximize catalyst stability, and minimize deleterious contaminantselectivity due to metal contaminants in resid feedstocks.

Resid feeds typically contain contaminant metals including Ni, V, Fe,Na, Ca, and others. Resid FCC for converting heavy resid feeds with highNi and V contaminants constitutes the fastest growing FCC segmentglobally. Both Ni and V catalyze unwanted dehydrogenation reactions, butNi is an especially active dehydrogenation catalyst. Ni significantlyincreases H₂ and coke yields. In addition to taking part in unwanteddehydrogenation reactions, V comes with other major concerns as it ishighly mobile under FCC conditions and its interaction with the zeolitedestroys its framework structure, which manifests itself as increased H₂and coke yields, as well as lower zeolite surface area retention. Evensmall amounts (e.g., 1-5 ppm) of contaminant metals in the feed depositcumulatively on the catalyst and can result in high H₂ and coke yieldsduring FCC operation, which is a major concern for the refiningindustry.

Since the 1960s, most commercial fluid catalytic cracking catalysts havecontained zeolites as an active component. Such catalysts have taken theform of small particles, called microspheres, containing both an activezeolite component and a non-zeolite component in the form of a highalumina, silica-alumina (aluminosilicate) matrix. The active zeoliticcomponent is incorporated into the microspheres of the catalyst by oneof two general techniques. In one technique, the zeolitic component iscrystallized and then incorporated into microspheres in a separate step.In the second technique, the in situ technique, microspheres are firstformed and the zeolitic component is then crystallized in themicrospheres themselves to provide microspheres containing both zeoliticand non-zeolitic components. For many years a significant proportion ofcommercial FCC catalysts used throughout the world have been made by insitu synthesis from precursor microspheres containing kaolin that hadbeen calcined at different severities prior to formation intomicrospheres by spray drying. U.S. Pat. No. 4,493,902 (“the '902patent”), incorporated herein by reference in its entirety, disclosesthe manufacture of fluid cracking catalysts comprisingattrition-resistant microspheres containing high Y zeolite, formed bycrystallizing sodium Y zeolite in porous microspheres composed ofmetakaolin and spinel. The microspheres in the '902 patent contain morethan about 40%, for example 50-70% by weight Y zeolite. Such catalystscan be made by crystallizing more than about 40% sodium Y zeolite inporous microspheres composed of a mixture of two different forms ofchemically reactive calcined clay, namely, metakaolin (kaolin calcinedto undergo a strong endothermic reaction associated withdehydroxylation) and kaolin clay calcined under conditions more severethan those used to convert kaolin to metakaolin, i.e., kaolin claycalcined to undergo the characteristic kaolin exothermic reaction,sometimes referred to as the spinel form of calcined kaolin. Thischaracteristic kaolin exothermic reaction is sometimes referred to askaolin calcined through its “characteristic exotherm.” The microspherescontaining the two forms of calcined kaolin clay are immersed in analkaline sodium silicate solution, which is heated, until the maximumobtainable amount of Y zeolite with faujasite structure is crystallizedin the microspheres.

Fluid cracking catalysts which contain silica-alumina or aluminamatrices are termed catalysts with “active matrix.” Catalysts of thistype can be compared with those containing untreated clay or a largequantity of silica, which are termed “inactive matrix” catalysts. Inrelation to catalytic cracking, despite the apparent disadvantage inselectivity, the inclusion of aluminas or silica-alumina has beenbeneficial in certain circumstances. For instance when processing ahydrotreated/demetallated vacuum gas oil (hydrotreated VGO) the penaltyin non-selective cracking is offset by the benefit of cracking or“upgrading” the larger feed molecules which are initially too large tofit within the rigorous confines of the zeolite pores. Once “precracked”on the alumina or silica-alumina surface, the smaller molecules may thenbe selectively cracked further to gasoline material over the zeoliteportion of the catalyst. While one would expect that this precrackingscenario might be advantageous for resid feeds, they are, unfortunately,characterized as being heavily contaminated with metals such as nickeland vanadium and, to a lesser extent, iron. When a metal such as nickeldeposits on a high surface area alumina such as those found in typicalFCC catalysts, it is dispersed and participates as highly active centersfor the catalytic reactions which result in the formation of contaminantcoke (contaminant coke refers to the coke produced discretely fromreactions catalyzed by contaminant metals). This additional coke exceedsthat which is acceptable by refiners. Loss of activity or selectivity ofthe catalyst may also occur if the metal contaminants (e.g. Ni, V) fromthe hydrocarbon feedstock deposit onto the catalyst. These metalcontaminants are not removed by standard regeneration (burning) andcontribute to high levels of hydrogen, dry gas and coke and reducesignificantly the amount of gasoline that can be made.

It would be desirable to provide FCC catalyst compositions, methods ofmanufacture, and FCC processes that reduce coke and hydrogen yields, inparticular, in feeds containing high levels of transition metals, forexample, in a resid feed.

SUMMARY

One aspect of the invention is directed to a fluid catalytic cracking(FCC) catalyst composition for processing resid feeds. Variousembodiments are listed below. It will be understood that the embodimentslisted below may be combined not only as listed below, but in othersuitable combinations in accordance with the scope of the invention.

In embodiment one, the catalyst composition comprises: catalyticmicrospheres containing a non-zeolitic component, 5 to 25% by weight ofa transition alumina, 20% to 65% by weight of a zeolite componentintergrown with the non-zeolitic component, a rare earth component and1% to 5% by weight of a phosphorus component on an oxide basis, whereinthe catalytic microspheres are obtained by forming rare earth-containingmicrospheres containing the non-zeolitic component, the transitionalumina, the zeolite component intergrown within the non-zeoliticcomponent, and yttria or a rare earth component, and further adding thephosphorus component to the rare earth-containing microspheres toprovide the catalytic microspheres, and wherein the FCC catalystcomposition is effective in preventing at least one of nickel andvanadium from increasing coke and hydrogen yields during cracking of ahydrocarbon.

Embodiment two is directed to a modification of catalyst compositionembodiment one, wherein the non-zeolitic component is selected from thegroup consisting of kaolinite, halloysite, montmorillonite, bentonite,attapulgite, kaolin, amorphous kaolin, metakaolin, mullite, spinel,hydrous kaolin, clay, gibbsite (alumina trihydrate), boehmite, titania,alumina, silica, silica-alumina, silica-magnesia, magnesia andsepiolite.

Embodiment three is directed to a modification of catalyst compositionembodiment one or two, wherein the phosphorus component is in the rangeof 2 wt. % to about 4.0 wt. % P₂O₅ on an oxide basis.

Embodiment four is directed to a modification of any of catalystcomposition embodiments one through three, wherein the rare-earthcomponent is selected from one or more of ceria, lanthana, praseodymia,and neodymia.

Embodiment five is directed to a modification of any of catalystcomposition embodiments one through four, wherein the rare earthcomponent is lanthana, and the lanthana is present in a range of 1 wt. %to about 5.0 wt. % on an oxide basis.

Embodiment six is directed to a modification of any of catalystcomposition embodiments one through five, wherein the phosphoruscomponent is present in a range of 2 wt. % and about 3.5 wt. % P₂O₅ onan oxide basis.

Embodiment seven is directed to a modification of any of catalystcomposition embodiments one through six, wherein the microsphere has aphosphorus level of about 2.5-3.5 wt. % P₂O₅ on an oxide basis and therare earth metal component is present in an amount of about 2-3 wt. % onan oxide basis.

Another aspect of the invention is directed to a method of cracking ahydrocarbon feed under fluid catalytic cracking conditions. Therefore,an eighth embodiment of the invention is directed to a method comprisingcontacting the hydrocarbon feed with the catalyst composition of any ofembodiments one through seven.

Embodiment nine is directed to a modification of method embodimenteight, wherein the non-zeolitic matrix component is selected from thegroup consisting of kaolinite, halloysite, montmorillonite, bentonite,attapulgite, kaolin, amorphous kaolin, metakaolin, mullite, spinel,hydrous kaolin, clay, gibbsite (alumina trihydrate), boehmite, titania,alumina, silica, silica-alumina, silica-magnesia, magnesia andsepiolite.

Embodiment ten is directed to a modification of method embodiment eightor nine, wherein the phosphorus component is in the range of 1 wt. % toabout 5.0 wt. % P₂O₅ on an oxide basis.

Embodiment eleven is directed to a modification of any of methodembodiments eight through ten, wherein the rare-earth component isselected from one or more of ceria, lanthana, praseodymia, and neodymia.

Embodiment twelve is directed to a modification of any of methodembodiments eight through eleven, wherein the rare earth component islanthana, and the lanthana is present in a range of 1 wt. % to about 5.0wt. % on an oxide basis.

Embodiment thirteen is directed to a modification of any of methodembodiments eight through twelve, wherein the microsphere has aphosphorus level of about 2.5 to 3.5 wt. % P₂O₅ on an oxide basis, andthe rare-earth metal component is present in an amount of about 2-3 wt.%, based on the weight of the catalyst.

Another aspect of the invention is directed to a method of manufacturingan FCC catalyst. Therefore, a fourteenth embodiment of the invention isdirected to a method comprising pre-forming a precursor microspherecomprising a non-zeolitic material and alumina; in situ crystallizing azeolite on the pre-formed microsphere to provide a zeolite-containingmicrosphere; adding a rare earth component to the zeolite-containingmicrosphere to provide a rare-earth-containing microsphere; and adding aphosphorus component to the rare earth-containing precursor microsphereto provide a catalytic microsphere.

Embodiment fifteen is directed to a modification of method embodimentfourteen, wherein the phosphorus component is added by contact withdiammonium phosphate.

Embodiment sixteen is directed to a modification of method embodimentfourteen or fifteen, wherein the rare earth component compriseslanthana, wherein the lanthana is added by ion exchange.

Embodiment seventeen is directed to a modification of any of methodembodiments fourteen through sixteen, further comprising adding aphosphorus component to the zeolite-containing microsphere.

Embodiment eighteen is directed to a modification of any of methodembodiments fourteen through seventeen, wherein the rare earth componentand the phosphorus component are added sequentially in separate steps.

Embodiment nineteen is directed to a modification of any of methodembodiments fourteen through eighteen, wherein the method comprisesadding a portion of the phosphorus component, then ion exchanging therare earth component and then adding an additional phosphorus component.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph comparing the hydrogen yields of cracking catalystsaccording to one or more embodiments and comparative catalysts uponcracking a heavy aromatic feed;

FIG. 2 is a graph comparing the contaminant coke yields of crackingcatalysts according to one or more embodiments and comparative catalystsupon cracking a heavy aromatic feed;

FIG. 3 is a graph comparing the hydrogen yields of cracking catalystsaccording one or more embodiments and comparative catalysts uponcracking a light feed; and

FIG. 4 is a graph comparing the contaminant coke yields of crackingcatalysts according to one or more embodiments and comparative catalystsupon cracking a light aromatic feed.

DETAILED DESCRIPTION

Before describing several exemplary embodiments of the invention, it isto be understood that the invention is not limited to the details ofconstruction or process steps set forth in the following description.The invention is capable of other embodiments and of being practiced orbeing carried out in various ways.

Embodiments of the present invention provide a FCC catalyst usingphosphorus-modified microspheres, which, according to one or moreembodiments, can be made by spray drying a mixture of mullite, hydrouskaolin, boehmite, and a silicate binder, followed by the in situcrystallization of zeolite Y, and then ion exchange, phosphorus loadingand calcination. Phosphorus modification of FCC catalyst microspheresnot only results in lower hydrogen and coke yields but also results inhigher zeolite surface area retention rates when processing hydrocarbonfeeds, particularly resid feeds contaminated with transition metals,namely Ni and V.

According to one or more embodiments, a catalyst composition is providedwhich exhibits higher performance due to the interaction of thephosphate species with contaminant metals. The phosphate speciesprevents contaminant metals from interfering with catalyst selectivity,reducing coke and hydrogen yields, and enhancing zeolite stability.

With respect to the terms used in this disclosure, the followingdefinitions are provided.

As used herein, the term “catalyst” or “catalyst composition” or“catalyst material” refers to a material that promotes a reaction.

As used herein, the term “fluid catalytic cracking” or “FCC” refers to aconversion process in petroleum refineries wherein high-boiling,high-molecular weight hydrocarbon fractions of petroleum crude oils areconverted to more valuable gasoline, olefinic gases, and other products.

“Cracking conditions” or “FCC conditions” refers to typical FCC processconditions. Typical FCC processes are conducted at reaction temperaturesof 450° to 650° C. with catalyst regeneration temperatures of 600° to850° C. Hot regenerated catalyst is added to a hydrocarbon feed at thebase of a rise reactor. The fluidization of the solid catalyst particlesmay be promoted with a lift gas. The catalyst vaporizes and superheatsthe feed to the desired cracking temperature. During the upward passageof the catalyst and feed, the feed is cracked, and coke deposits on thecatalyst. The coked catalyst and the cracked products exit the riser andenter a solid-gas separation system, e.g., a series of cyclones, at thetop of the reactor vessel. The cracked products are fractionated into aseries of products, including gas, gasoline, light gas oil, and heavycycle gas oil. Some heavier hydrocarbons may be recycled to the reactor.

As used herein, the term “feed” or “feedstock” refers to that portion ofcrude oil that has a high boiling point and a high molecular weight. InFCC processes, a hydrocarbon feedstock is injected into the risersection of a FCC unit, where the feedstock is cracked into lighter, morevaluable products upon contacting hot catalyst circulated to theriser-reactor from a catalyst regenerator.

As used herein, the term “resid” refers to that portion of crude oilthat has a high boiling point and a high molecular weight and typicallycontains contaminant metals including Ni, V, Fe, Na, Ca, and others. Thecontaminant metals, particularly Ni and V, have detrimental effects oncatalyst activity and performance. In some embodiments, in a resid feedoperation one of Ni and V metals accumulate on the catalyst, and the FCCcatalyst composition is effective to contact nickel and vanadium duringcracking.

As used herein, the term “non-zeolitic component” refers to thecomponents of a FCC catalyst that are not zeolites or molecular sieves.As used herein, the non-zeolitic component can comprise binder andfiller. A non-zeolitic component may be referred to as the matrix.According to one or more embodiments, the “non-zeolitic component” canbe selected from the group consisting of clay, kaolinite, halloysite,montmorillonite, bentonite, attapulgite, kaolin, amorphous kaolin,metakaolin, mullite, spinel, hydrous kaolin, clay, gibbsite (aluminatrihydrate), boehmite, titania, alumina, silica, silica-alumina,silica-magnesia, magnesia and sepiolite. The non-zeolitic component canbe an aluminosilicate.

As used herein, the term “zeolite” refers to is a crystallinealuminosilicate with a framework based on an extensive three-dimensionalnetwork of oxygen ions and have a substantially uniform poredistribution.

As used herein, the term “intergrown zeolite” refers to a zeolite thatis formed by an in situ crystallization process.

As used herein, the term “in situ crystallized” refers to the process inwhich a zeolite is grown or intergrown directly on/in a microsphere andis intimately associated with the matrix or non-zeolitic material, forexample, as described in U.S. Pat. Nos. 4,493,902 and 6,656,347. Thezeolite is intergrown within the macropores of the microsphere, suchthat the zeolite is uniformly dispersed on the matrix or non-zeoliticmaterial.

As used herein, the terms “preformed microspheres” or “precursormicrospheres” refer to microspheres obtained by spray drying andcalcining a non-zeolitic matrix component and a transition alumina.

As used herein, the term “zeolite-containing microsphere” refers to amicrosphere obtained by in situ crystallizing a zeolite material onpre-formed precursor microspheres. The zeolite is intergrown directlyon/in the macropores of the precursor microsphere such that the zeoliteis intimately associated and uniformly dispersed on the matrix ornon-zeolitic material.

As used herein, the term “rare-earth-containing microsphere” refers tomicrospheres that include an in situ crystallized zeolite (i.e.zeolite-containing microsphere) and are treated with a rare earthcomponent such that the rare earth component is intimately associatedwith the matrix or non-zeolitic material.

As used herein, the term “catalytic microsphere” refers to microspheresthat are obtained by addition of a phosphorus component to arare-earth-containing microsphere. Catalytic microspheres contain anon-zeolitic component (or matrix material), a transition alumina, an insitu crystallized zeolite, a rare-earth component, and a phosphoruscomponent.

“Transition alumina” is defined as any alumina which is intermediatebetween the thermodynamically stable phases of gibbsite, bayerite,boehmite, pseudoboehmite and nordstrandite on one end of the spectrumand alpha alumina or corundum on the other. Such transition aluminas maybe viewed as metastable phases. A scheme of the transformation sequencecan be found in the text: Oxides and Hydroxides of Aluminum by K. Wefersand C. Misra; Alcoa Technical Paper No. 19, revised; copyright AluminumCompany of America Laboratories, 1987.

FCC catalyst compositions which include a zeolite component have acatalytically active crystallized aluminosilicate material, such as, forexample, a large-pore zeolite crystallized on or in a microspherecomprising non-zeolitic material. Large pore zeolite cracking catalystshave pore openings of greater than about 7 Angstroms in effectivediameter. Conventional large-pore molecular sieves include zeolite X;REX; zeolite Y; Ultrastable Y (USY); Rare Earth exchanged Y (REY); RareEarth exchanged USY (REUSY); Dealuminated Y (DeAl Y); Ultrahydrophobic Y(UHPY); and/or dealuminated silicon-enriched zeolites, e.g., LZ-210.According to one or more embodiments, the FCC catalyst comprisescatalytic microspheres comprising a crystalline aluminosilicate materialselected from zeolite Y, ZSM-20, ZSM-5, zeolite beta, zeolite L; andnaturally occurring zeolites such as faujasite, mordenite and the like,and a non-zeolitic component. These materials may be subjected toconventional treatments, such calcinations and ion exchange with rareearths to increase stability.

Microspheres comprising hydrous kaolin clay and/or metakaolin, adispersible boehmite, optionally spinel and/or mullite, and a sodiumsilicate or silica sol binder can be prepared in accordance with thetechniques described in U.S. Pat. No. 6,716,338, which is incorporatedherein by reference. For example, the catalysts can be made bycrystallizing the desired amount of sodium Y zeolite in porousmicrospheres composed of a mixture of two different forms of chemicallyreactive calcined clay, namely, metakaolin and spinel. The microspherescontaining the two forms of calcined kaolin clay are immersed in analkaline sodium silicate solution, which is heated, until the maximumobtainable amount of Y zeolite is crystallized in the microspheres. Theamount of zeolite according to embodiments of the invention is in therange of 20% to 95%, or 30% to 60%, or 30% to 45% by weight based on theweight of the FCC catalyst composition.

Preparation of Phosphorus Containing Microspheres

A first aspect of the invention is directed to a fluid catalyticcracking (FCC) catalyst composition for resid feed refining. In one ormore embodiments, the FCC catalyst composition comprises catalyticmicrospheres containing a non-zeolitic component, 5 to 25% by weight ofa transition alumina, 20% to 95% by weight of a zeolite componentintergrown with the non-zeolitic component, a rare earth component and1% to 5% by weight of a phosphorus component on an oxide basis. In oneor more embodiments, the catalytic microspheres are obtained by formingrare-earth containing microspheres containing the non-zeoliticcomponent, the transition alumina, the zeolite component intergrownwithin the non-zeolitic component, and the rare earth component, andfurther adding the phosphorus component to the rare earth-containingmicrospheres to provide the catalytic microspheres. In one or moreembodiments, the FCC catalyst composition is effective to prevent atleast one of nickel and vanadium from increasing coke and hydrogenyields during cracking of a hydrocarbon.

An aqueous slurry of finely divided hydrous kaolin, kaolin that has beencalcined through its characteristic exotherm, and binder is prepared.The slurry can optionally contain boehmite. In specific embodiments, thehydrous kaolin, calcined kaolin and binder are premixed in one tank andfed to the spray drier from one line. When present, an aqueous aluminaslurry, peptized such as with formic acid is introduced from a separateline immediately prior to when the whole mix enters the spray drier.Other mixing and injection protocols may also be useful. For example, apolymer dispersed alumina, for example dispersed with Flosperse® can beused in the process. The final slurry solids are about 30-70 wt. %. Theaqueous slurry is then spray dried to obtain microspheres comprising asilica bonded mixture of hydrated kaolin, boehmite and kaolin that hasbeen calcined at least substantially through its characteristic exotherm(spinel, or mullite, or both spinel and mullite). The preformedmicrospheres have average particle diameters that are typical ofcommercial fluid catalytic cracking catalysts, e.g., 65-85 microns.Suitable spray drying conditions are set forth in the '902 patent.

The reactive kaolin of the slurry to form the preformed microspheres canbe formed of hydrated kaolin or calcined hydrous kaolin (metakaolin) ormixtures thereof. The hydrous kaolin of the feed slurry can suitably beeither one or a mixture of ASP® 600 or ASP® 400 kaolin, derived fromcoarse white kaolin crudes. Finer particle size hydrous kaolins can alsobe used, including those derived from gray clay deposits, such as LHTpigment. Purified water-processed kaolin clays from Middle Ga. can alsobe used. Calcined products of these hydrous kaolins can be used as themetakaolin component of the feed slurry.

A commercial source of powdered kaolin calcined through the exotherm maybe used as the spinel component. Hydrated kaolin clay is converted tothis state by calcining the kaolin at least substantially completelythrough its characteristic exotherm. (The exotherm is detectable byconventional differential thermal analysis, DTA). After completion ofcalcination, the calcined clay is pulverized into finely dividedparticles before being introduced into the slurry that is fed to a spraydryer. The spray dried product is repulverized. The surface area (BET)of typical spinel form kaolin is low, e.g., 5-10 m²/g; however, whenthis material is placed in a caustic environment such as that used forcrystallization, silica is leached, leaving an alumina-rich residuehaving a high surface area, e.g. 100-200 m²/g (BET).

Mullite can also be used as a matrix component. Mullite is made byfiring clay at temperatures above 2000° F. For example M93 mullite maybe made from the same kaolin clay source as Ansilex 93, used for thepreparation of spinel component. Mullite can also be made from otherkaolin clays. Mullite may also be made from Kyanite clay. HeatingKyanite clay to a high temperature of 3000° F., provides a morecrystalline, purer mullite in the calcined product than that obtainedfrom kaolin clay.

According to one or more embodiments, the alumina used to prepare thepreformed microspheres is a highly dispersible boehmite. Dispersibilityof the hydrated alumina is the property of the alumina to disperseeffectively in an acidic media such as formic acid of pH less than about3.5. Such acid treatment is known as peptizing the alumina. Highdispersion is when 90% or more of the alumina disperses into particlesless than about 1 micron. When this dispersed alumina solution is spraydried with the kaolin and binder, the resulting preformed microspherecontains uniformly distributed alumina throughout the microsphere.

After spray drying, the preformed microspheres are washed and calcinedat a temperature and for a time (e.g., for two to four hours in a mufflefurnace at a chamber temperature of about 1500° to 1550° F.) sufficientto convert the hydrated clay component of the microspheres tometakaolin, leaving the spinel component of the microspheres essentiallyunchanged. In specific embodiments, the calcined preformed microspherescomprise about 30 to 70% by weight metakaolin, about 10 to 50% by weightspinel and/or mullite and 5 to about 25% by weight transition phasealumina. In one or more embodiments, the transition phase aluminacomprises one or more of gamma, delta, theta, eta, or chi phase. Inspecific embodiments, the surface area (BET, nitrogen) of thecrystalline boehmite (as well as the transition alumina) is below 150m²/g, specifically below 125 m²/g, and more specifically, below 100m²/g, for example, 30-80 m²/g.

When boehmite is incorporated into FCC catalysts, it can serve as a trapfor transition metals, especially Ni. Without intending to be bound bytheory, it is thought that boehmite inhibits the dehydrogenationactivity of Ni in hydrocarbon feeds by converting it to Ni-aluminate(NiAl₂O₄). In one or more embodiments, the catalyst comprises from about0.5% to 20% by weight of boehmite. The transition alumina phase thatresults from the dispersible boehmite during the preparative procedureand which forms a portion of the matrix of the final catalyst,passivates the Ni and V that are deposited onto the catalyst during thecracking process, especially during cracking of heavy resid feeds.

The preformed or precursor microspheres are reacted with zeolite seedsand an alkaline sodium silicate solution, substantially as described inU.S. Pat. No. 5,395,809, the teachings of which are incorporated hereinby cross-reference. The zeolite component is intergrown with the matrixcomponent. The microspheres are crystallized to a desired zeolitecontent (for example, 20-65% by weight, or 30-60% by weight, or 30-45%by weight), filtered, washed, ammonium exchanged, exchanged withrare-earth cations if required, calcined, exchanged a second time withammonium ions, and calcined a second time if required, and optionallyion-exchanged. The silicate for the binder can be provided by sodiumsilicates with SiO₂ to Na₂O ratios of from 1.5 to 3.5, morespecifically, ratios of from 2.00 to 3.22.

In specific embodiments, the crystallized aluminosilicate materialcomprises from about 20 to about 65 wt. % zeolite Y, for example, 30% to65% by weight, or 30% to 45% by weight, expressed on the basis of theas-crystallized sodium faujasite form zeolite. In one or moreembodiments, the Y-zeolite component of the crystalline aluminosilicate,in their sodium form, have a crystalline unit cell size range of between24.64-24.73 Å, corresponding to a SiO₂/Al₂O₃ molar ratio of theY-zeolite of about 4.1-5.2.

After crystallization by reaction in a seeded sodium silicate solution,the preformed microspheres contain crystalline Y-zeolite in the sodiumform. Sodium cations in the microspheres are replaced with moredesirable cations. This may be accomplished by contacting themicrospheres with solutions containing ammonium, yttrium cations, rareearth cations or combinations thereof. In one or more embodiments, theion exchange step or steps are carried out so that the resultingcatalyst contains less than about 0.7%, more specifically less thanabout 0.5% and even more specifically less than about 0.2%, by weightNa₂O. After ion exchange, the microspheres are dried. Rare earth levelsin the range of 0.1% to 12% by weight, specifically 1-5% by weight, andmore specifically 2-3% by weight are contemplated. More specifically,examples of rare earth compounds are the nitrates of lanthanum, cerium,praseodymium, and neodymium. Typically, the amount of rare earth addedto the catalyst as a rare earth oxide will range from about 1 to 5%,typically 2-3 wt. % rare earth oxide (REO).

Following ammonium and rare earth exchange, the rare-earth containingmicrosphere catalyst composition is further modified with phosphorus toprovide a catalytic microsphere. The microsphere catalyst compositioncan be contacted with a medium containing an anion, for example, adihydrogen phosphate anion (H₂PO₄ ⁻), a dihydrogen phosphite anion(H₂PO₃ ⁻) or mixtures thereof for a time sufficient to compositephosphorus, with the catalyst. Suitable amounts of phosphorus to beincorporated in the catalyst include at least about 0.5 weight percent,specifically at least about 0.7 weight percent, more specifically fromabout 1 to 4 weight percent, calculated as P₂O₅, based on the weight ofthe zeolite plus whatever matrix remains associated with the zeolite.

The anion is derived from a phosphorus-containing component selectedfrom inorganic acids of phosphorus, salts of inorganic acids ofphosphorus, and mixtures thereof. Suitable phosphorus-containingcomponents include phosphorus acid (H₃PO₃), phosphoric acid (H₃PO₄),salts of phosphorus acid, salts of phosphoric acid and mixtures thereof.Although any soluble salts of phosphorus acid and phosphoric acid, suchas alkali metal salts and ammonium salts may be used to provide thedihydrogen phosphate or phosphite anion, in specific embodiments,ammonium salts are used since the use of alkali metal salts wouldrequire subsequent removal of the alkali metal from the catalyst. In oneembodiment, the anion is a dihydrogen phosphate anion derived frommonoammonium phosphate, diammonium phosphate and mixtures thereof.Contact with the anion may be performed as at least one step ofcontacting or a series of contacts which may be a series of alternatingand successive calcinations and dihydrogen phosphate or phosphite anioncontacting steps. In specific embodiments, up to about 3-4% P₂O₅ contentis achieved in a single step.

Contact of the anion with the zeolite and kaolin derived matrix issuitably conducted at a pH ranging from about 2 to about 8. The lower pHlimit is selected to minimize loss of crystallinity of the zeolite. Theupper pH limit appears to be set by the effect of the anionconcentration. Suitable concentrations of the dihydrogen phosphate ordihydrogen phosphite anion in the liquid medium range from about 0.2 toabout 10.0 weight percent anion.

In the above described procedure, the rare earth ion exchange isperformed prior to addition of the phosphorus component. However, itwill be understood that according to one or more embodiments, it may bedesirable to add a phosphorus component prior to rare earth ionexchange. In other embodiments, it may be desirable to add thephosphorus component both prior to rare earth ion exchange and afterrare earth ion exchange.

According to one or more embodiments, the catalyst comprises from about1% to about 5% phosphorus (P₂O₅), including 1, 2, 3, 4, and 5%. Inspecific embodiments, the catalyst comprises at least 2% P₂O₅. Aspecific range is 2.5 to 3.5 wt. % P₂O₅.

Without intending to be bound by theory, it is thought that thesequential addition of a rare earth component followed by addition of aphosphorus component produces microspheres that are surface areastabilized. In other words, the catalytic microspheres are stabilized toresist loss of surface area during FCC cracking. It is believed that ifthe phosphorus component is added prior to the addition of the rareearth component, and no further phosphorus is added, the microspheresare not surface area stabilized. As used herein, the term “surface areastabilized” refers to catalytic microspheres that have an aged surfacearea that exceeds the aged surface area of catalytic microspheres inwhich the rare earth component and phosphorus component were not addedsequentially. In one or more embodiments, a phosphorus component isadded prior to the addition of a rare earth component, and then, afterthe rare earth component is added, an additional phosphorus component isadded, such that the total phosphorus content is from about 1% to about5% P₂O₅, including 1, 2, 3, 4, 5%.

According to one or more embodiments, the selectivity benefits of addingphosphorus result in enhanced metals passivation, particularly whenphosphorus is added to a catalyst that contains transition alumina. Inparticular, in addition to surface area stabilization, phosphorusaddition to a transition alumina-containing catalyst providessignificant benefits, including lower hydrogen and coke yield and higheractivity. Lowering hydrogen yields is beneficial in wet gascompressor-limited processes.

Subsequent to the rare earth exchange and phosphorus addition, catalystcomposition is then dried and then calcined at a temperature of from800°-1200° F. The conditions of the calcination are such that the unitcell size of the zeolite crystals is not significantly reduced.Typically, the drying step, after rare earth exchange is to remove asubstantial portion of the water contained within the catalyst.

The rare earth oxide-containing catalyst, subsequent to calcination, isnow further ion exchanged, typically by ammonium ions to, again, reducethe sodium content to less than about 0.5 wt. % Na₂O. The ammoniumexchange can be repeated to ensure that the sodium content is reduced toless than 0.5 wt. % Na₂O. Typically, the sodium content will be reducedto below 0.2 wt. % as Na₂O. Subsequent to ammonium exchange, the reducedsodium catalyst containing the Y-type zeolite and the kaolin derivedmatrix can be contacted again with a medium containing the phosphoruscompounds as described above, with respect to the first phosphorustreatment. The medium contains sufficient phosphorus to provide acontent of phosphorus as P₂O₅ of at least 2.0 wt. % and, more typically,an amount of phosphorus as P₂O₅ of 2.8 to 3.5 wt. % relative to thecatalyst, including zeolite and kaolin derived matrix. Temperatures andpH conditions for the second phosphorus treatment are as in the firsttreatment described above. After phosphorus treatment, the impregnatedcatalyst is calcined again at temperatures of from 700°-1500° F.

The catalysts of the invention can also be used in conjunction withadditional V-traps. Thus, in one or more embodiments, the catalystfurther comprises a V-trap. The V-trap can be selected from one or moreconventional V-traps including, but not limited to, MgO/CaO Withoutintending to be bound by theory, it is thought that MgO/CaO interactswith V₂O₅ through an acid/base reaction to give vanadates.

A second aspect of the present invention pertains to a method ofcracking a hydrocarbon feed under fluid catalytic cracking conditions.In one or more embodiments, the method comprises contacting thehydrocarbon feed with the phosphorus modified catalyst of one or moreembodiments. In one or more embodiments, the hydrocarbon feed is a residfeed. In one or more embodiments, in a resid feed operation, one of Niand V metals accumulate on the catalyst, and the FCC catalystcomposition is effective to contact nickel and vanadium during cracking,thus reducing coke and hydrogen yields.

Conditions useful in operating FCC units utilizing catalyst of theinvention are known in the art and are contemplated in using thecatalysts of the invention. These conditions are described in numerouspublications including Catal. Rev.-Sci. Eng., 18 (1), 1-150 (1978),which is herein incorporated by reference in its entirety. The catalystsof one or more embodiments are particularly useful in cracking residuumand resid-containing feeds.

A further aspect of the present invention pertains to a method ofmanufacturing an FCC catalyst composition. In one or more embodiments,the method comprises pre-forming a precursor microsphere comprisingnon-zeolitic matrix material and alumina; in situ crystallizing zeoliteon the pre-formed microsphere to provide a zeolite-containingmicrosphere; adding a rare earth component to the zeolite-containingmicrosphere to provide a rare-earth-containing microsphere; and adding aphosphorus component to the rare-earth-containing microsphere to providea catalytic microsphere. In one or more embodiments, the phosphorus isadded by reacting/contacting the rare-earth-containing microsphere withdiammonium phosphate. In specific embodiments, the rare earth componentcomprises lanthana, and the lanthana is introduced to thezeolite-containing microsphere by ion exchange.

In one or more embodiments, the method of manufacturing furthercomprises adding a phosphorus component to the zeolite-containingmicrosphere. In specific embodiments, the rare earth and the phosphoruscomponent are added sequentially in separate steps.

In other embodiments, the method comprises adding a portion of thephosphorus component, then ion exchanging with the rare earth component,and then adding an additional phosphorus component. It is noted thatadding the rare earth component and the phosphorus component at the sametime may deleteriously affect catalytic activity.

The invention is now described with reference to the following examples.

EXAMPLES Example 1

Calcined kaolin (mullite) (36.6 kg) slurry made to 49% solids was addedto 59% solids hydrous kaolin (25.9 kg), while mixing, using a Cowlesmixer. Next a 56% solids boehmite alumina (14 kg) slurry was slowlyadded to the mixing clay slurry and was allowed to mix for more thanfive minutes. The mixture was screened and transferred to a spray dryerfeed tank. The clay/boehmite slurry was spray dried with sodium silicateinjected in-line just prior to entering the atomizer. Sodium silicate(20.2 kg, 3.22 modulus) was used at a metered ratio of 1.14 liter/minslurry: 0.38 liter/min silicate. The target particle size for themicrospheres was 80 microns. Binder sodium was removed from the formedmicrospheres by slurrying the microspheres for thirty minutes andmaintaining the pH from 3.5-4 using sulfuric acid. Finally, the acidneutralized microspheres were dried and calcined at 1350-1500° F. fortwo hours. The microspheres were processed to grow 60-65% zeolite Yusing an in situ crystallization process. A sample of crystallized NaYmicrospheres (250 g) was ion exchanged to achieve a Na₂O of 2.0% usingammonium nitrate. Rare earth was then added to 2 wt. % REO. The rareearth exchanged sample was calcined at 1000° F. for 2 hours to stabilizethe catalyst and facilitate zeolitic sodium removal. After calcinations,a series of ammonium nitrate ion exchanges was performed to <0.2 wt. %Na₂O. Finally, with the reduced sodium, a second calcination was done at1100° F. for 2 hours in order to further stabilize the catalyst andreduce unit cell size. To evaluate the resid catalyst in circulatingriser unit, a sample (20 kg) was prepared following the process using a25 gallon reactor vessel and pan filters for the ion exchange and Ptreatments. Calcinations were completed in covered trays in muffleovens. The catalyst composition is further impregnated with 3000 ppm ofnickel and 2500 ppm of vanadium and aged under cyclic reducing andoxidizing conditions in the presence of steam at between 1350-1500° F.The catalytic activity and selectivity of the catalyst composition isdetermined using Advanced Cracking Evaluation (ACE) reactors andprotocols.

Example 2

Calcined kaolin (mullite) (36.6 kg) slurry made to 49% solids was addedto 59% solids hydrous kaolin (25.9 kg), while mixing, using a Cowlesmixer. Next a 56% solids boehmite alumina (14 kg) slurry was slowlyadded to the mixing clay slurry and was allowed to mix for more thanfive minutes. The mixture was screened and transferred to a spray dryerfeed tank. The clay/boehmite slurry was spray dried with sodium silicateinjected in-line just prior to entering the atomizer. Sodium silicate(20.2 kg, 3.22 modulus) was used at a metered ratio of 1.14 liter/minslurry:0.38 liter/min silicate. The target particle size for themicrospheres was 80 microns. Binder sodium was removed from the formedmicrospheres by slurrying the microspheres for thirty minutes andmaintaining the pH from 3.5-4 using sulfuric acid. Finally, the acidneutralized microspheres were dried and calcined at 1350-1500° F. fortwo hours. The microspheres were processed to grow 60-65% zeolite Yusing an in situ crystallization process. A sample of crystallized NaYmicrospheres (250 g) was ion exchanged to achieve a Na₂O of 2.0% usingammonium nitrate. The sodium adjusted sample was treated with phosphorusto 1.5% P₂O₅. Rare earth (lanthanum) was then added to 2 wt. % REO. Thephosphorus and rare earth exchanged sample was calcined at 1000° F. for2 hours to stabilize the catalyst and facilitate zeolitic sodiumremoval. After calcinations, a series of ammonium nitrate ion exchangeswas performed to <0.2 wt. % Na₂O. Once at desired sodium level, a secondphosphorus treatment was carried out to increase the total P₂O₅ to 3%.Finally, with the reduced sodium, a second calcination was done at 1100°F. for 2 hours in order to further stabilize the catalyst and reduceunit cell size. To evaluate the P modified resid catalyst in circulatingriser unit, a sample (20 kg) was prepared following the process using a25 gallon reactor vessel and pan filters for the ion exchange and Ptreatments. Calcinations were completed in covered trays in muffleovens. The catalyst composition is further impregnated with 3000 ppm ofnickel and 2500 ppm of vanadium and aged under cyclic reducing andoxidizing conditions in the presence of steam at between 1350-1500° F.The catalytic activity and selectivity of the catalyst composition isdetermined using Advanced Cracking Evaluation (ACE) reactors andprotocols.

Example 3

The catalyst of Example 1 is combined with a separate particle vanadiumtrap prior to metals impregnation and deactivation and the catalyticactivity and selectivity of the catalyst composition is determined usingAdvanced Cracking Evaluation (ACE) reactors and protocols.

Example 4

The catalyst of Example 2 is combined with a separate particle vanadiumtrap prior to metals impregnation deactivation and the catalyticactivity and selectivity of the catalyst composition is determined usingAdvanced Cracking Evaluation (ACE) reactors and protocols.

Results

Characterization and catalytic testing results at 70% conversion arepresented in Table

TABLE 4 ACE results On a Resid Feed Example 2 -Example 1 Example 4Example 3 (Inven- (Compar- (Inven- (Compar- tion) ative) tion) ative) H₂0.29 0.38 0.20 0.30 Propylene 4.34 4.15 4.57 4.56 LPG 14.42 14.21 15.0814.68 Total C4 16.47 16.41 17.01 16.76 Gasoline 43.98 43.72 44.25 44.03LCO 15.29 15.98 15.65 15.92 HCO 14.71 14.02 14.35 14.08 Coke 9.54 9.888.74 9.21 Cat/Oil 3.06 2.81 3.44 3.34 Activity 4.52 4.56 4.27 4.25 @ C/O= 7.7 Conversion 81.88 82.02 81.04 80.94 @ C/O = 7.7

ACE testing of the catalyst impregnated with nickel and vanadium revealthat at 70 wt. % conversion relative to Example 1, Example 2 gives: 24%lower hydrogen, 3% lower coke, along with 0.6% higher gasoline, and 4.5%higher propylene, with nearly equivalent LPG and total C4 at equivalentactivity.

Example 3 combines Example 1 with a separate particle vanadium trap, andExample 4 combines Example 2 with a separate particle vanadium trap. Theresults indicate that the catalyst of Example 4 offers benefits over thecatalyst of Example 3 including: 33% lower hydrogen and 5% lower coke.Examples 5 and 6

The Examples 3 and 4 described above were prepared according to theprocedure explained above and were tested in a pilot-scale FCC unitusing two different types of feeds after loading with contaminant metals(3000 ppm Ni and 2500 ppm V) followed by hydrothermal deactivation.

FIGS. 1-2 present the results for coke and H₂ for a resid feed. FIGS.3-4 present the results for coke and H₂ for a lighter (VGO) feed.

Example 7 Double Stage Phosphorus Addition

Following the process in Example 2, a sample was prepared having a rareearth content of 2 percent by weight and phosphorus total was 3% P₂O₅.

Example 8 Single Stage Phosphorus Addition

Similar to the process in Example 2, a sample was prepared, whereby aphosphorus addition was employed only during the second applicationstage as described in example 2.Rare earth was 2% REO and phosphorustotal was 3% P₂O₅ added in one stage.

Example 9 Comparative Example (No Phosphorus)

Using the microspheres of Example 1, an FCC catalyst was prepared havinga rare earth content of 2 percent by weight.

The three samples (Examples 7, 8, and 9) were prepared for ACE catalyticevaluation using the following protocol:

Presteamed at 1350° F./2 hours/100% steam

Impregnated with 3000 ppm Ni and 3000 ppm V

Steamed 1500° F./5 hour/90% steam and 10% air

Catalytic evaluation is presented in Table V. The results are shown atconstant 70 wt. % conversion.

TABLE 2 ACE Results Example 9 Example 7 Example 8 0% Single Stage 3%Double Stage 3% P₂O₅ P₂O₅ P₂O₅ H₂ 1.34 1.09 1.23 Propylene 4.07 4.304.19 LPG 13.19 14.62 14.18 Gasoline 42.88 42.91 43.07 LCO 17.48 15.8516.57 HCO 12.53 14.16 13.43 Coke 10.34 9.22 9.32 Cat/Oil 7.43 6.34 6.75Activity 2.39 2.60 2.53 @ C/O = 7.7 Conversion 70.47 72.22 71.64 @ C/O =7.7

Examples 7 and 8 show preferred hydrogen and coke yields compared toExample 9.

All references, including publications, patent applications, andpatents, cited herein are hereby incorporated by reference for allpurposes to the same extent as if each reference were individually andspecifically indicated to be incorporated by reference and were setforth in its entirety herein.

The use of the terms “a” and “an” and “the” and similar referents in thecontext of describing the materials and methods discussed herein(especially in the context of the following claims) are to be construedto cover both the singular and the plural, unless otherwise indicatedherein or clearly contradicted by context. Recitation of ranges ofvalues herein are merely intended to serve as a shorthand method ofreferring individually to each separate value falling within the range,unless otherwise indicated herein, and each separate value isincorporated into the specification as if it were individually recitedherein. All methods described herein can be performed in any suitableorder unless otherwise indicated herein or otherwise clearlycontradicted by context. The use of any and all examples, or exemplarylanguage (e.g., “such as”) provided herein, is intended merely to betterilluminate the materials and methods and does not pose a limitation onthe scope unless otherwise claimed. No language in the specificationshould be construed as indicating any non-claimed element as essentialto the practice of the disclosed materials and methods.

Reference throughout this specification to “one embodiment,” “certainembodiments,” “one or more embodiments” or “an embodiment” means that aparticular feature, structure, material, or characteristic described inconnection with the embodiment is included in at least one embodiment ofthe invention. Thus, the appearances of the phrases such as “in one ormore embodiments,” “in certain embodiments,” “in one embodiment” or “inan embodiment” in various places throughout this specification are notnecessarily referring to the same embodiment of the invention.Furthermore, the particular features, structures, materials, orcharacteristics may be combined in any suitable manner in one or moreembodiments.

Although the invention herein has been described with reference toparticular embodiments, it is to be understood that these embodimentsare merely illustrative of the principles and applications of thepresent invention. It will be apparent to those skilled in the art thatvarious modifications and variations can be made to the method andapparatus of the present invention without departing from the spirit andscope of the invention. Thus, it is intended that the present inventioninclude modifications and variations that are within the scope of theappended claims and their equivalents.

What is claimed is:
 1. A fluid catalytic cracking (FCC) catalystcomposition for processing resid feeds comprising: catalyticmicrospheres containing a non-zeolitic component, 5 to 25% by weight ofa transition alumina, 20% to 65% by weight of a zeolite componentintergrown with the non-zeolitic component, a rare earth component and1% to 5% by weight of a phosphorus component on an oxide basis, whereinthe catalytic microspheres are obtained by forming rare earth-containingmicrospheres containing the non-zeolitic component, the transitionalumina, the zeolite component intergrown within the non-zeoliticcomponent, and yttria or a rare earth component, and further adding thephosphorus component to the rare earth-containing microspheres toprovide the catalytic microspheres, and wherein the FCC catalystcomposition is effective in preventing at least one of nickel andvanadium from increasing coke and hydrogen yields during cracking of ahydrocarbon.
 2. The FCC catalyst composition of claim 1, wherein thenon-zeolitic component is selected from the group consisting ofkaolinite, halloysite, montmorillonite, bentonite, attapulgite, kaolin,amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin, clay,gibbsite (alumina trihydrate), boehmite, titania, alumina, silica,silica-alumina, silica-magnesia, magnesia and sepiolite.
 3. The FCCcatalyst composition of claim 2, wherein the phosphorus component is inthe range of 2 wt. % to about 4.0 wt. % P₂O₅ on an oxide basis.
 4. TheFCC catalyst composition of claim 3, wherein the rare-earth component isselected from one or more of ceria, lanthana, praseodymia, and neodymia.5. The FCC catalyst composition of claim 4, wherein the rare earthcomponent is lanthana, and the lanthana is present in a range of 1 wt. %to about 5.0 wt. % on an oxide basis.
 6. The FCC catalyst composition ofclaim 5, wherein the phosphorus component is present in a range of 2 wt.% and about 3.5 wt. % P₂O₅ on an oxide basis.
 7. The FCC catalystcomposition of claim 6, wherein the microsphere has a phosphorus levelof about 2.5-3.5 wt. % P₂O₅ on an oxide basis and the rare earth metalcomponent is present in an amount of about 2-3 wt. % on an oxide basis.8. A method of cracking a hydrocarbon feed under fluid catalyticcracking conditions, the method comprising contacting the hydrocarbonfeed with the catalyst of claim
 1. 9. The method of claim 8, wherein thenon-zeolitic matrix component is selected from the group consisting ofkaolinite, halloysite, montmorillonite, bentonite, attapulgite, kaolin,amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin, clay,gibbsite (alumina trihydrate), boehmite, titania, alumina, silica,silica-alumina, silica-magnesia, magnesia and sepiolite.
 10. The methodof claim 9, wherein the phosphorus component is in the range of 1 wt. %to about 5.0 wt. % P₂O₅ on an oxide basis.
 11. The method of claim 10,wherein the rare-earth component is selected from one or more of ceria,lanthana, praseodymia, and neodymia.
 12. The method of claim 11, whereinthe rare earth component is lanthana, and the lanthana is present in arange of 1 wt. % to about 5.0 wt. % on an oxide basis.
 13. The method ofclaim 12, wherein the microsphere has a phosphorus level of about 2.5 to3.5 wt. % P₂O₅ on an oxide basis, and the rare-earth metal component ispresent in an amount of about 2-3 wt. %, based on the weight of thecatalyst.
 14. A method of manufacturing an FCC catalyst comprising:pre-forming a precursor microsphere comprising a non-zeolitic materialand alumina; in situ crystallizing a zeolite on the pre-formedmicrosphere to provide a zeolite-containing microsphere; adding a rareearth component to the zeolite-containing microsphere to provide arare-earth-containing microsphere; and adding a phosphorus component tothe rare earth-containing precursor microsphere to provide a catalyticmicrosphere.
 15. The method of claim 14, wherein the phosphoruscomponent is added by contact with diammonium phosphate.
 16. The methodof claim 15, wherein the rare earth component comprises lanthana,wherein the lanthana is added by ion exchange.
 17. The method of claim16, further comprising adding a phosphorus component to thezeolite-containing microsphere.
 18. The method of claim 16, wherein therare earth component and the phosphorus component are added sequentiallyin separate steps.
 19. The method of claim 28, wherein the methodcomprises adding a portion of the phosphorus component, then ionexchanging the rare earth component and then adding an additionalphosphorus component.